Suture material for wounds based on methylidene malonate

Abstract

A method for the suture of wounds, includes applying a sufficient quantity of a biocompatible, bio-adhesive mixture with at least 50% by weight of a methylidene malonate-based composition containing:40 to 100% by weight of at least one methylidene malonate of formula (I): in which:A and B independently represent a group (a) or (b):in which R1 and R2 independently represent a linear or branched alkyl group with 1 to 6 carbon atoms, n is an integer between 1 and 5, and at least one of A and B represents a (b) group;and/or one or more methylidene malonate oligomers with a molecular weight less than or equal to 6,000 and including recurrent units of formula (II):in which A and B are as defined above; and0 to 60% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000 and including recurrent units of formula (II).

What is claimed is:  
     
       1. A method for the suture of wounds, comprising applying within a wound a sufficient quantity of a biocompatible, bio-adhesive mixture comprising at least 50% by weight of a methylidene malonate-based composition containing: 
       40 to 100% by weight of at least one methylidene malonate of formula (I)                    
        in which:  
       A and B independently represent a group (a) or (b):                    
       in which R 1  and R 2  independently represent a linear or branched alkyl group with 1 to 6 carbon atoms, n is an integer between 1 and 5, and at least one of A and B represents a (b) group; 
       and/or one or more methylidene malonate oligomers with a molecular weight less than or equal to 6,000 and including recurrent units of formula (II):                    
       in which A and B are as defined above; and  
       0 to 60% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000 and including recurrent units of formula (II).  
     
     
       2. A method according to  claim 1 , wherein in said formulae (I) and (II): 
       A represents a group (a) in which R 1  represents an alkyl group with 1 to 6 carbon atoms, and  
       B represents a group (b) in which R 2  represents an alkyl group with 1 to 6 carbon atoms, and n is a number equal to 1.  
     
     
       3. A method according to  claim 2 , wherein in said formulae (I) and (II): 
       A represents a group (a) in which R 1  represents an ethyl group; and  
       B represents a group (b) in which R 2  represents an ethyl group and n is a number equal to 1.  
     
     
       4. A method according to  claim 1 , wherein said methylidene malonate-based composition contains: 
       50 to 90% by weight of at least one methylidene malonate oligomer with a molecular weight less than or equal to 6,000 and including recurrent units of formula (II), and  
       10 to 50% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000,  
       said mixture having a glass transition temperature that is less than or equal to 0° C.  
     
     
       5. A method according to  claim 4 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight that less than or equal to 3,000 and consisting of recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000.  
     
     
       6. A method according to claims  5 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight between 300 and 1,000 and including recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight between 12,000 and 25,000.  
     
     
       7. A method according to  claim 4 , wherein said mixture contains up to 50% by weight of at least one constituent other than the methylidene malonate-based composition, and selected from the group consisting of: 
       polycyanoacrylates;  
       polyalkylmethacrylates;  
       biocompatible polyurethanes;  
       polyoxyalkylenes;  
       polyaminoacids;  
       polylactates;  
       polylactate-co-glycolates; and  
       polyvinylalcohols.  
     
     
       8. A method according to  claim 7 , wherein said at least one constituent is present, at least in part, in the form of monomer units associated with the methylidene malonate units of formula (II), in a copolymer. 
     
     
       9. A method according to  claim 4 , wherein said mixture contains up to 20% by weight of at least one constituent other than the methylidene malonate-based composition, and selected from the group consisting of: 
       polycyanoacrylates;  
       polyalkylmethacrylates;  
       biocompatible polyurethanes;  
       polyoxyalkylenes;  
       polyaminoacids;  
       polylactates;  
       polylactate-co-glycolates; and  
       polyvinylalcohols.  
     
     
       10. A method according to  claim 1 , wherein said mixture contains at least 90% by weight of said methylidene malonate-based composition. 
     
     
       11. A method for the suture of wounds comprising: 
       a) preheating to a temperature above its softening temperature, a biocompatible, bioadhesive mixture comprising at least 50% by weight of a methylidene malonate-based composition containing:  
       40 to 100% by weight of at least one methylidene malonate of formula (I)                    
        in which:  
       A and B independently represent a group (a) or (b):                    
       in which R 1  and R 2  independently represent a linear or branched alkyl group with 1 to 6 carbon atoms, n is an integer between 1 and 5, and at least one of A and B represents a (b) group;  
       and/or one or more methylidene malonate oligomers with a molecular weight less than or equal to 6,000 and including recurrent units of formula (II):                    
       in which A and B are as defined above; and  
       0 to 60% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000 and including recurrent units of formula (II);  
       b) applying within a wound a sufficient quantity of the preheated mixture.  
     
     
       12. A method according to  claim 11 , wherein the methylidene malonate-based composition contains: 
       50 to 90% by weight of at least one methylidene malonate oligomer with a molecular weight less than or equal to 6,000 and consisting of recurrent units of formula (II), and  
       10 to 50% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000,  
       said mixture having a glass transition temperature that s less than or equal to 0° C.  
     
     
       13. A method according to  claim 12 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight that less than or equal to 3,000 and including recurrent units of formula (II),  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000.  
     
     
       14. A method according to  claim 13 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight between 300 and 1,000 and including recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight between 12,000 and 25,000.  
     
     
       15. A method according to  claim 12 , wherein said mixture contains up to 20% by weight of at least one constituent other than the methylidene malonate-based composition, and selected from the group consisting of: 
       polycyanoacrylates;  
       polyalkylmethacrylates;  
       biocompatible polyurethanes;  
       polyoxyalkylenes;  
       polyaminoacids;  
       polylactates;  
       polylactate-co-glycolates; and  
       polyvinylalcohols.  
     
     
       16. A method according to  claim 15 , wherein said at least one constituent is present, at least in part, in the form of monomer units associated with the methylidene malonate units of formula (II), in a copolymer. 
     
     
       17. A method according to  claim 11 , wherein said mixture contains at least 90% by weight of said methylidene malonate-based composition. 
     
     
       18. A material comprising at least 90% by weight of a methylidene malonate composition containing: 
       50 to 90% by weight of at least one methylidene malonate oligomer with a molecular weight less than or equal to 6,000 and including recurrent units of formula (II):                    
        in which:  
       A and B independently represent a group (a) or (b):                    
       in which R 1  and R 2  independently represent a linear or branched alkyl group with 1 to 6 carbon atoms, n is an integer between 1 and 5, and at least one of A and B represents a (b) group; and  
       10 to 50% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000,  
       said material having a glass transition temperature that is less than or equal to 0° C.  
     
     
       19. A material which comprising at least 90% by weight of a methylidene malonate composition containing: 
       50 to 90% by weight of at least one methylidene malonate oligomer with a molecular weight less than or equal to 3,000 and including recurrent units of formula (II):                    
        in which:  
       A and B independently represent a group (a) or (b):                    
       in which R 1  and R 2  independently represent a linear or branched alkyl group with 1 to 6 carbon atoms, n is an integer between 1 and 5, and at least one of A and B represents a (b) group; and  
       10 to 50% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000,  
       said material having a glass transition temperature that is less than or equal to 0° C.  
     
     
       20. A material according to  claim 19 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight that less than or equal to 3,000 and including recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000.  
     
     
       21. Material according to  claim 20 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight between 300 and 1,000 and including recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight between 12,000 and 25,000.  
     
     
       22. A material according to  claim 19 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight that less than or equal to 3,000 and including recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight greater than 9,000.  
     
     
       23. A material for the suture of wounds, comprising a biocompatible, bio-adhesive mixture comprising at least 50% by weight of a methylidene malonate-based composition containing: 
       40 to 100% by weight of at least one methylidene malonate of formula (I)                    
        in which:  
       A and B independently represent a group (a) or (b):                    
       in which R 1  and R 2  independently represent a linear or branched alkyl group with 1 to 6 carbon atoms, n is an integer between 1 and 5, and at least one of A and B represents a (b) group;  
       and/or at least one methylidene malonate oligomer with a molecular weight less than or equal to 6,000 and including recurrent units of formula (II):                    
       in which A and B are as defined above;  
       0 to 60% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000 and including recurrent units of formula (II).  
     
     
       24. A material according to  claim 23 , wherein in said formulae (I) and (II): 
       A represents a group (a) in which R 1  represents an alkyl group with 1 to 6 carbon atoms,  
       B represents a group (b) in which R 2  represents an alkyl group with 1 to 6 carbon atoms, and n is a number equal to 1.  
     
     
       25. A material according to  claim 24 , wherein in said formulae (I) and (II): 
       A represents a group (a) in which R 1  represents an ethyl group; and  
       B represents a group (b) in which R 2  represents an ethyl group and n is a number equal to 1.  
     
     
       26. A material according to  claim 23 , wherein the methylidene malonate-based composition contains: 
       50 to 90% by weight of at least one methylidene malonate oligomer with a molecular weight less than or equal to 6,000 and consisting of recurrent units of formula (II), and  
       10 to 50% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000,  
       said material having a glass transition temperature that is less than or equal to 0° C.  
     
     
       27. A material according to  claim 26 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight that less than or equal to 3,000 and including recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight greater than 6,000.  
     
     
       28. A material according to  claim 27 , wherein the methylidene malonate-based composition contains: 
       55 to 65% by weight of at least one methylidene malonate oligomer with a molecular weight between 300 and 1,000 and including recurrent units of formula (II), and  
       35 to 45% by weight of at least one methylidene malonate polymer with a molecular weight between 12,000 and 25,000.  
     
     
       29. A material according to  claim 26 , comprising up to 50% by weight of at least one constituent other than said methylidene malonate-based composition, and selected from the group consisting of: 
       polycyanoacrylates;  
       polyalkylmethacrylates;  
       biocompatible polyurethanes;  
       polyoxyalkylenes;  
       polyaminoacids;  
       polylactates;  
       polylactate-co-glycolates; and  
       polyvinylalcohols.  
     
     
       30. A material according to  claim 29 , wherein said at least one constituent is present in the form of monomer units associated with the methylidene malonate units of formula (II), in a copolymer. 
     
     
       31. A material according to  claim 26 , comprising up to 20% by weight of at least one constituent other than said methylidene malonate-based composition, and selected from the group consisting of: 
       polycyanoacrylates;  
       polyalkylmethacrylates;  
       biocompatible polyurethanes;  
       polyoxyalkylenes;  
       polyaminoacids;  
       polylactates;  
       polylactate-co-glycolates; and  
       polyvinylalcohols.  
     
     
       32. A material according to  claim 23 , comprising at least 90% by weight of said methylidene malonate-based composition .